Reactive diluent for radiation curing of film-forming polymers

Various film-forming monomers are employed as coating materials and can be cured either thermally or by radiation in the presence of a free radical photoinitiator. Acrylates and methacrylates and vinyl lactams are suitable for this purpose. However, certain vinyl lactam monomers, e.g. N-vinyl caprolactams, alkyl substituted N-vinylpyrrolidones and acrylate oligomers are solids or semi-solid resins which are difficult to handle or to incorporate in reaction mixtures or to provide a uniform distribution of the monomeric or oligomeric species.

Accordingly, it is an object of this invention to provide a liquid reactive diluent for free radical induced radiation polymerizations of acrylate or methacrylate monomers and oligomers, which may be economically and conveniently prepared from commercially available compounds.

The reactive diluent should be capable of modifying the crosslinked density and flexibility of acrylate polymerized coatings, and be stable against discoloration and which improves adhesion to vinyl surfaces.

Yet another object is to provide a polymerizable diluent system capable of forming a terpolymeric protective coating on a substrate.

Still another object is to provide a substrate coated with an improved protective coating.

These and other objects of this invention will become apparent from the following description and disclosure.

THE INVENTION

In accordance with this invention there is provided a reactive diluent mixture or blend suitable for use in radiation curing of a(meth)acrylate monomer or oligomer which consists essentially of between 25 and 90 wt. % of a N-vinyl lactam having from 6 to 9 carbon atoms and between 10 and 75 wt. % of a non-cyclic N-vinyl amide having from 3 to 7 carbon atoms. The use of said reactive diluent mixture during radiation curing of a(meth)acrylate monomer or oligomer and a method for curing the resulting composition are also objects of the invention. The above mixture, in the presence of a free radical and a polymerizable acrylate monomer or oligomer can be subjected to radiation curing on a substrate to provide a color stable, acid and base resistant protective coating thereon. The above blend is added and mixed with the polymerizable film-forming monomer or oligomer until a uniform mixture is obtained. The free radical polymerization of the acrylate-diluent mixture can be initiated in the presence of a photoinitiator or by electron beam where no initiator is required.

The film-forming polymerizable compounds of this invention include multifunctional acrylates and methacrylates such as urethane dimethacrylate, urethane diacrylate, di- and tri- acrylates or methacrylates of ethylene glycol, diethylene glycol di- and tri- acrylates or methacrylates and higher polyethylene glycol polyacrylates or methacrylates, 1,3- and 1,4-dibutanediol diacrylate or methacrylate, poly- methacrylate urethane, epoxy acrylate, polyester acrylate monomers and oligomers as well as mixtures of the above monomers and/or oligomers. In order to preserve in predominance the characteristics of the acrylate in the polymeric product, the above blend is incorporated in a concentration of between about 10 and about 40 wt. % of the total monomeric mixture; although concentrations of up to 85% are acceptable when predominance of those characteristics is unimportant.

Preferred blends of the present reactive diluent comprise between about 55 and about 85 wt. % vinyl caprolactam or vinylpyrrolidone and between about 15 to 45 wt. % N-vinyl formamide or N-vinyl-N-methyl-acetamide which provide liquid mixtures conveniently employed in radiation curing.

The present reactive diluent blend can be introduced into the reactor in admixture with the free radical photoinitiator, a surfactant which may be required, another non-reactive excipient or in admixture with the curable film-forming acrylate monomer or oligomer.

Curing of the present compositions can be effected in less than 1 second at or about room temperature by exposure to a source of radiation, e.g., between about 100 and about 800 millijoules/cm² of UV light, between about 0.5 and about 5 megarads of electron beam exposure or equivalent radiation exposures of gamma ray and X-ray. Laser emissions can also be employed to effect curing. The above reactive diluent or compositions containing the reactive diluent are suitable for coating on a substrate such as glass, ceramic, wood, plastic, metal, vinyl, leather and paper in a thickness of from 0.00254 to 0.127 mm. (0.1 to 5 mils).

Suitable photoinitiators for the present invention are aromatic acyl compounds and the preferred photoinitiators are those having the formulas disclosed in Tables 1-6 of The European Coatings Journal 5/1988 on pages 350-352, i.e. <chemistry id="chem0001" num="0001"><img file="EP0739366B1_D0001.tif" /></chemistry> where m has a value of 0 or 1; R is alkyl, -N(CH₃)₂, -C₆H₅, -O-C₆H₅, -CH₂SO₃Na or -CH₂N(CH₃)₃Cl and A is <chemistry id="chem0002" num="0002"><img file="EP0739366B1_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0739366B1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0739366B1_D0004.tif" /></chemistry> where B is hydrogen or methyl, R₁ and R₃ are independently hydrogen, C₁ to C₂ alkyl or alkoxy, R₂ is hydrogen, hydroxy or phenyl and R₄ is C₁ to C₂ alkyl or phenyl; or <chemistry id="chem0005" num="0005"><img file="EP0739366B1_D0005.tif" /></chemistry> where R₅ is chlorine or alkyl. The preferred photoinitiators of this invention are the hydroxy substituted monophenyl ketones.

The concentration of initiator in the monomeric mixture is between about 0.05 and about 5 wt. % based on total monomer.

Illustrative of a typical formulation which provides color stability, adhesion to vinyl substrates and a low freezing or solidification point includes: <ul id="ul0001" list-style="none" compact="compact"><li>1-85 wt. % of the present reactive diluent blend,</li><li>99-25 wt. % film-forming monomer and</li><li>0.5-5 wt. % free radical photoinitiator.</li></ul>

The film-forming compositions are easily prepared as a solution or slurry of photoinitiator, preferably in a concentration of from about 1 to about 3 wt. %, and film-forming monomers followed by the addition of the present reactive diluent mixture in the desired amount with continued stirring until a clear or homogeneous solution is obtained. This procedure is normally carried out under about ambient conditions; although elevated temperatures up to about 100°C. can be employed when desired.

Optional adjuvants may be added to the composition to supply additional wetting characteristics. Suitable optional additives include wetting agents, e.g. fluorinated alkyl ester surfactants, ethoxylates of alkyl phenols, fatty alcohols, alpha-olefins, and other excipients, as desired.

The general techniques for exposing coating surfaces to radiation for curing are well known and the present compositions are cured in a conventional manner.

Optional features of the invention are defined in the dependent claims.

Having thus described the invention, reference is now had to the following Examples which illustrate specific and preferred embodiments, but which are not to be construed as limiting to the scope of the invention as more broadly described above and in the appended claims.

EXAMPLES 1-3

Comparison of Vinyl Caprolactam (VCPL), N-vinyl formamide (NVF), and a 50/50 VCPL/NVF blend as reactive diluents in the following UV curable coating formulation

Components in Table I were charged into an amber bottle and mixed at room temperature until homogeneous. The formulation viscosity was measured at 25°C. Coatings were cast on the indicated substrates (0.0254 mm) (1 mil) coating thickness) using a #12 Mayer bar and cured by a UV exposure of 200 mJ/cm². Coating properties were determined, using standardized test methods, immediately after UV exposure. Results are summarized below: <tables id="tabl0001" num="0001"><table frame="all"><title>TABLE 1</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">COMPOSITION</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">3</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Urethane Acrylate</entry><entry namest="col2" nameend="col2" align="char" char=".">75.0</entry><entry namest="col3" nameend="col3" align="char" char=".">75.0</entry><entry namest="col4" nameend="col4" align="char" char=".">75.0</entry></row><row><entry namest="col1" nameend="col1" align="left">VCPL</entry><entry namest="col2" nameend="col2" align="char" char=".">25.0</entry><entry namest="col3" nameend="col3" align="char" char=".">-</entry><entry namest="col4" nameend="col4" align="char" char=".">-</entry></row><row><entry namest="col1" nameend="col1" align="left">NVF</entry><entry namest="col2" nameend="col2" align="char" char=".">-</entry><entry namest="col3" nameend="col3" align="char" char=".">25.0</entry><entry namest="col4" nameend="col4" align="char" char=".">-</entry></row><row><entry namest="col1" nameend="col1" align="left">VCPL/NVF:50/50</entry><entry namest="col2" nameend="col2" align="char" char=".">-</entry><entry namest="col3" nameend="col3" align="char" char=".">-</entry><entry namest="col4" nameend="col4" align="char" char=".">25.0</entry></row><row><entry namest="col1" nameend="col1" align="left">1-hydroxycyclohexyl phenyl ketone</entry><entry namest="col2" nameend="col2" align="char" char=".">3.0</entry><entry namest="col3" nameend="col3" align="char" char=".">3.0</entry><entry namest="col4" nameend="col4" align="char" char=".">3.0</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Viscosity (cps)</entry><entry namest="col2" nameend="col2" align="char" char=".">12500</entry><entry namest="col3" nameend="col3" align="char" char=".">5200</entry><entry namest="col4" nameend="col4" align="char" char=".">6850</entry></row></tbody></tgroup><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">CURED FILM PROPERTIES</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Hardness</entry><entry namest="col2" nameend="col2" align="char" char=".">3H</entry><entry namest="col3" nameend="col3" align="char" char=".">2H</entry><entry namest="col4" nameend="col4" align="char" char=".">2H</entry></row><row><entry namest="col1" nameend="col1" align="left">% Adhesion to Polyester</entry><entry namest="col2" nameend="col2" align="char" char=".">100</entry><entry namest="col3" nameend="col3" align="char" char=".">100</entry><entry namest="col4" nameend="col4" align="char" char=".">100</entry></row><row><entry namest="col1" nameend="col1" align="left">% Adhesion to Vinyl</entry><entry namest="col2" nameend="col2" align="char" char=".">100</entry><entry namest="col3" nameend="col3" align="char" char=".">0</entry><entry namest="col4" nameend="col4" align="char" char=".">25</entry></row><row><entry namest="col1" nameend="col1" align="left">Double MEK Rubs</entry><entry namest="col2" nameend="col2" align="char" char=".">&gt;100</entry><entry namest="col3" nameend="col3" align="char" char=".">&gt;100</entry><entry namest="col4" nameend="col4" align="char" char=".">&gt;100</entry></row><row><entry namest="col1" nameend="col1" align="left">Solvent Resistance¹</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">   conc. NH₄OH</entry><entry namest="col2" nameend="col2" align="char" char=".">0</entry><entry namest="col3" nameend="col3" align="char" char=".">2</entry><entry namest="col4" nameend="col4" align="char" char=".">0</entry></row><row><entry namest="col1" nameend="col1" align="left">   4% Acetic Acid</entry><entry namest="col2" nameend="col2" align="char" char=".">0</entry><entry namest="col3" nameend="col3" align="char" char=".">0</entry><entry namest="col4" nameend="col4" align="char" char=".">0</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Contact Angle of Water²</entry><entry namest="col2" nameend="col2" align="char" char=".">75.0</entry><entry namest="col3" nameend="col3" align="char" char=".">65.7</entry><entry namest="col4" nameend="col4" align="char" char=".">74.8</entry></row></tbody></tgroup><tgroup cols="4" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><tbody valign="top"><row><entry namest="col1" nameend="col4" align="justify">¹ ASTM D-1308, 16 hrs. at room temperature 0 = no attack, 5 = severe attack</entry></row><row><entry namest="col1" nameend="col4" align="justify">² Measured by goniometer</entry></row></tbody></tgroup></table></tables>

From this example it can be seen that NVF provides the lowest viscosity to provide good leveling in the coating; however, the cured film has poor adhesion to vinyl substrates and is attacked by concentrated base. The low contact angle of water also indicates that this coating is water sensitive, i.e. it absorbs water and does not provide water fastness. Other objections to NVF are poor shelf life stability when stored under ambient conditions coupled with rapid increase of APHA color and tendency to homopolymerize during storage. VCPL, a crystalline product, is not effective at reducing viscosity of the film-forming monomer. The VCPL/NVF blend provides low viscosity, excellent resistance to water, acid and base, and shows acceptable adhesion to vinyl surfaces.

EXAMPLES 4-7

To optimize adhesion to vinyl surfaces, several VCPL/NVF ratios were evaluated in the above coating formulation. Blends containing greater than 50% VCPL show excellent adhesion. <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Example No.</entry><entry namest="col2" nameend="col2" align="center">VCPL/NVF ratio</entry><entry namest="col3" nameend="col3" align="center">% Adhesion to Vinyl</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">4</entry><entry namest="col2" nameend="col2" align="right">0/100</entry><entry namest="col3" nameend="col3" align="right">0</entry></row><row><entry namest="col1" nameend="col1" align="center">5</entry><entry namest="col2" nameend="col2" align="right">50/50</entry><entry namest="col3" nameend="col3" align="right">25</entry></row><row><entry namest="col1" nameend="col1" align="center">6</entry><entry namest="col2" nameend="col2" align="right">75/25</entry><entry namest="col3" nameend="col3" align="right">100</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">7</entry><entry namest="col2" nameend="col2" align="right">90/10</entry><entry namest="col3" nameend="col3" align="right">100</entry></row></tbody></tgroup></table></tables>

EXAMPLES 8-14

Vinyl caprolactam (VCPL) is a crystalline solid at room temperature (freezing point = 35°C.) ; accordingly, it must be gradually melted by warming to 50°C. so as to facilitate handling during the coating preparation. VCPL/N-vinyl amide blends remain liquid at room temperature thus providing significantly improved handling. Various amido and non-amido comonomers for VCPL were evaluated as to their ability to reduce freezing or solidification point (SP). Vinyl amides were clearly the most effective monomers evaluated since VCPL blends of these amides containing about 15% NVF or VMA (N-vinyl-N-methyl acetamide) have solidification points significantly below room temperature.

Figure 1 summarizes these findings and compares ethoxy ethoxy ethylacrylate shown by line <img file="EP0739366B1_D0006.tif" />; octadecyl acrylate shown by line <img file="EP0739366B1_D0007.tif" />; pentaerythritol triacrylate indicated by line <img file="EP0739366B1_D0008.tif" />; phenoxyethyl acrylate indicated by line <img file="EP0739366B1_D0009.tif" />; triethylene glycol divinyl ether indicated by line <img file="EP0739366B1_D0010.tif" />; N-vinyl formamide shown by line <img file="EP0739366B1_D0011.tif" />and N-vinyl-N-methyl acetamide shown by line <img file="EP0739366B1_D0012.tif" />.

EXAMPLE 15

It was found that NVF discolors quickly when stored under ambient conditions; however, blending NVF with VCPL (75/25 proportion) significantly improves color stability as shown in Figure 2 where NVF is indicated by line <img file="EP0739366B1_D0013.tif" />VCPL by line <img file="EP0739366B1_D0014.tif" /> and the NVF/VCPL blend by line <img file="EP0739366B1_D0015.tif" />.

It is to be understood that other reactive diluent blends including N-vinylpyrrolidone, N-vinyl lower alkyl caprolactams and other non-cyclic N-vinyl amides within the above definitions, e.g. N-vinyl succinimide can be substituted in Example 3 to provide stable solutions suitable for radiation curing with free radical initiators.